CN1036546A - Preparation contains the polydichlorophosphazenes method for compositions of a certain proportion of cyclic oligomer and the composition that utilizes this method to obtain - Google Patents

Preparation contains the polydichlorophosphazenes method for compositions of a certain proportion of cyclic oligomer and the composition that utilizes this method to obtain Download PDF

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CN1036546A
CN1036546A CN89101879A CN89101879A CN1036546A CN 1036546 A CN1036546 A CN 1036546A CN 89101879 A CN89101879 A CN 89101879A CN 89101879 A CN89101879 A CN 89101879A CN 1036546 A CN1036546 A CN 1036546A
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composition
oligopolymer
cyclic oligomer
polydichlorophosphazenes
formula
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塞尔日·博迪尔
让-保罗·尚布列蒂
盖伊·帕尼兹
菲利普·波丁
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Arkema France SA
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Atochem SA
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/097—Compounds containing nitrogen and non-metals and optionally metals containing phosphorus atoms
    • C01B21/098—Phosphonitrilic dihalides; Polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/097—Compounds containing nitrogen and non-metals and optionally metals containing phosphorus atoms
    • C01B21/098—Phosphonitrilic dihalides; Polymers thereof
    • C01B21/0986—Phosphonitrilic dichlorides; Polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/10—Halides or oxyhalides of phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
    • C08G79/025—Polyphosphazenes

Abstract

The present invention relates to the polydichlorophosphazenes method for compositions that a kind of preparation has the cyclic oligomer of certain content.
The control of cyclic oligomer content is to realize by changing the monomeric concentration of carrying out polycondensation in the described monomer solution.
The invention still further relates to the some compositions that contains a certain proportion of cyclic oligomer.

Description

Preparation contains the polydichlorophosphazenes method for compositions of a certain proportion of cyclic oligomer and the composition that utilizes this method to obtain
The present invention relates to prepare the method for the polydichlorophosphazenes that contains a certain proportion of cyclic oligomer, also relate to the polydichlorophosphazenes composition that contains the described cyclic oligomer of certain proportion, also further relate to by the described polydichlorophosphazenes composition in front and carry out the polychlorophosphnitrile composition that substitution reaction obtains.
The method for making of the polyphosphonitrile that general formula is following:
Figure 891018794_IMG3
R wherein 1And R 2Can be identical or different in same unit or different units, they represent group as alkoxyl group, aryloxy, alkyl, aryl, sulphur or amine, and the polyphosphonitrile method for making is carried out usually in two steps, the polydichlorophosphazenes of preparation following formula earlier,
Figure 891018794_IMG4
N＝PCl 2 （Ⅱ）
Then, use R 1And R 2The group of representative replaces the chlorine atom in the formula II polymkeric substance, obtains the polyphosphonitrile of formula I.
The polydichlorophosphazenes of formula II can make according to two kinds of technology usually, and a kind of is ring-type chlordene three phosphonitriles by following formula set out (for example United States Patent (USP) 3,370,020 in the described method of H.R.Allcock)
Figure 891018794_IMG6
Dichlor-phosphoryl base trichlorine phosphonitrile another kind of as the described use following formula of R de Jaeger in French Patent 79.24307,83.11264 or in the french application of having announced 2,571,710,
The perhaps dichloro sulphur phosphoryl trichlorine phosphonitrile of following formula.
When using a kind of method in back, polycondensation is followed and is emitted POCl 3Or PSCl 3
In order to obtain the rubber-like polyphosphonitrile, suggestion (United States Patent (USP) 3,943,088,4,107,108,4,124,557 and 4,152,314) linear poly-dichlorides phosphorus nitrile with the formula II is used in combination with line style or cyclic phosphazene oligopolymer, described oligopolymer play a part softening agent and can with the polymer-compatible of formula I and II.
These line styles or cyclic oligomer can be respectively by replacing the chlorination tripolyphosphazene with the used same substituent of polymkeric substance itself or four polyphosphonitriles prepare.The oligopolymer that replaces then can be mixed with the polymer phase of formula I when cooperating.
When preparing polydichlorophosphazenes with the cyclic trimer method, for fear of crosslinked polymer, must reach at 50% o'clock at transformation efficiency and stop polymerization, this has caused exist (both the making after removing cyclic trimer) of big weight oligomers.After substitution reaction, these molecular weight are generally 700～500,000 oligopolymer extracts by selective dissolution and separates, and can be with needed per-cent and polymkeric substance remix.
(these two kinds of products are following with simple molecular formula P to the present invention relates to a kind of usefulness dichlor-phosphoryl base trichlorine phosphonitrile and/or dichloro sulphur phosphoryl trichlorine phosphonitrile 2NXCl 5Expression, X represents O or S) directly produce the polydichlorophosphazenes method for compositions that contains the certain proportion cyclic oligomer.Also relate to these poly-two phosphazene compositions that contain the certain proportion oligopolymer and the polyphosphonitrile composition of replacement.
The inventive method is characterised in that by changing P in the solution that will carry out polycondensation 2NXCl 5Concentration control the ratio of cyclic oligomer.
The composition (itself also being another object of the present invention) that uses the inventive method to obtain is characterised in that they comprise the cyclic oligomer of a kind of polydichlorophosphazenes and one or more following formulas,
Wherein n is that 3～5(is included) oligopolymer and the P that wants in the solution of polycondensation 2NXCl 5Concentration is inversely proportional to.
The present invention be more particularly directed to contain the composition of oligopolymer shown in one or more formula III (n=3,4 or 5 in the formula), but it obviously is not precluded within the composition that wherein can find higher order oligomers, promptly n＞5 in the formula III for example can reach 6～10.
Usually, the composition that is directly obtained by such solution polycondensation does not have unreacted monomer basically.In these compositions, The present invention be more particularly directed to contain in general the composition (measuring) of 1.5～50% oligopolymer with method described in the example 1 with respect to polydichlorophosphazenes and oligopolymer, oligopolymer contains the oligopolymer of the n=3 of 2～10% the formula III of having an appointment, the oligopolymer of the oligopolymer of about 15～35% n=4 and about 55～75% n=5.
Be understood that these observations are the compositions that directly obtain about polycondensation in dielectric solvent, and always might change the oligomer of composition afterwards.
In implementing the inventive method, find PXCl from emitting 3The per-cent of oligopolymer stops to increase in the time of can not surveying, and this is to occur later in 10% of about whole polycondensation time usually.The per-cent of oligopolymer finishes to remain unchanged substantially up to polycondensation then.The per-cent in the method for the invention verified, that cyclic oligomer exists in the polydichlorophosphazenes composition that obtains in the time of can very accurately being adjusted in this method of enforcement by the ratio of selecting initial monomer/solvent of introducing.Obviously in polycondensation process particularly at PXCl 3The back (as in French Patent 2,571,710 in indication) that disappears, add again 1 time or several times certain amount of solvent do not exceed the scope of the invention yet.(this replacements operation is known, so does not constitute purpose of the present invention) composition itself contains the cyclic oligomer of having regulated per-cent in advance after polydichlorophosphazenes replaces operation, i.e. softening agent, and no longer use complement operation.
Purely in order to illustrate, can use and can persist in the solvent in the composition that method thus obtains in the method for the invention, can select from hydrocarbon and containing the chlorine derivative of this class hydrocarbon especially with aromatic series feature.Can singly use or mix in this kind solvent that uses, what particularly point out is benzene, naphthalene, biphenyl, chlorobenzene, dichlorobenzene, trichlorobenzene, tetrachlorobenzene, pentachlorobenzene, Perchlorobenzene, chlorinated naphthalene, chlorodiphenyl, particularly trichloro biphenyl.
Usually, P 2NXCl 5Condensation temperature can be preferably between 210～300 ℃ at 200～350 ℃.
Accord with the method for under this temperature, implementing of the present invention, can prepare some compositions that contain oligopolymer (as specified in the following example 1) usually, P in solution 2NXCl 5Concentration is lower than that oligomer can be up to 50% at P under 10% the situation 2NXCl 5Concentration was near 100% o'clock, and oligomer reduces to 1.5%.Usually this concentration can 0.1% and be roughly 100% between change.
In order to illustrate,, per-cent and P at cyclic oligomer (all prods of the formula III of n=3, n=4 and n=5) can be proposed purely for 270 ℃ condensation temperature 2NOCl 5Starting point concentration between following relationship arranged:
Log (oligopolymer %)=-1.43 * 10 -2(P 2NOCl 5%)+1.726
(correction coefficient: 0.996)
This relation of description of drawings.
The polydichlorophosphazenes composition that makes by the described method in front can replace according to known technology, as reacting with phenates or alcoholate.The same formation of these poly-organophosphorus cyanide compositions purpose of the present invention.
Following example explanation the present invention.
Example 1
Polycondensation plant comprises the reactor that a band stirs, this reactor with the turning oil heating, reflux exchanger and constant temperature are housed at 140 ℃, reactor is connected to one and accepts POCl 3System, described system comprises a descending condenser and a graduated receiver.
894 gram (3.32 moles) P are housed in the reactor 2NOCl 5And be heated to 280 ℃.React after 4 hours POCl 3In fact no longer flow out.In this sampling and add 826.4 gram trichloro biphenyls in stage.Polycondensation 47 hours is by time (t) sampling.To each sample nucleus magnetic resonance 31 -P measures cyclic oligomer and polydichlorophosphazenes.
Point out below to distribute between trimerization, the four poly-and pentamers and these oligopolymer with respect to the distribution of polymkeric substance.Numerical value is all represented with the % of phosphorus, n 3%, n 4% and n 5% is provided by bottom's relation.
(with n 3Or n 4Or n 5Corresponding peak integration)/(total ∑ i)
Sum ∑ i is equivalent to n 3, n 4And n 5The integration summation at peak.
∑ Ni%=is (corresponding to n 3, n 4And n 5The ∑ of integration at peak NiSum)/(∑ Ni+ corresponding to the integration at the peak of polymkeric substance)
These table data show that fs in polycondensation is (until POCl 3Stopping to discharge) 100% concentration produces the cyclic oligomer (∑ ni% about 2.5 ± 0.5) of certain percentage, and it is constant that this per-cent keeps in polycondensation process, and molecular weight rises, and no crosslinked, this is to make it to become possibility owing to solubilizing agent.
Example 2
Replace 894 gram P with the same monomer of 100 grams 2NOCl 5Again carry out the test of example 1, under various temperature and multiple concentration, carry out polycondensation.Same usefulness nucleus magnetic resonance- 31P analyzes.
The results are shown in following table.
In this table, t(hour) numerical value shown in the hurdle is roughly than emitting POCl 3Many one times of required time.
(1) concentration is represented the ratio of solution weight with monomer weight.
It is to the measured in solution of carrying out polycondensation at first.
This table needs following explanation:
With example 2,3 and 4 is one side, for comparing on the other hand, shows under given temperature P with example 8,9,10,11 and 12 2NOCl 5Concentration is low more, and (∑ ni%) is high more for the content of oligopolymer.
Oligopolymer per-cent trends towards raising with temperature, this phenomenon more obvious at low temperatures (under identical monomer concentration).
Contrast each example of comprehensively testing again 5,6 and 7, show the repeatability of this method.

Claims (11)

1, contain the polydichlorophosphazenes method for compositions of certain proportion cyclic oligomer by the directly preparation of setting out of dichlor-phosphoryl base trichlorine phosphonitrile and/or dichloro sulphur phosphoryl trichlorine phosphonitrile, starting compound can be used molecular formula P 2NXCl 5Expression, wherein X represents O or S respectively, and described method is characterised in that, by changing P in the polycondensation solution 2NXCl 5Concentration control the per-cent of cyclic oligomer in the described composition.
2,, it is characterized in that cyclic oligomer comprises the product shown in the following formula according to the method for claim 1:
Wherein n is that 3～5(is included).
3, according to any one method in claim 1 or 2, it is characterized in that P 3NOCl 5Concentration between 0.1～100%.
4, according to any one method in the claim 1～3, it is characterized in that condensation temperature is between 200 and 350 ℃.
5,, it is characterized in that solvent is selected from the hydrocarbon with aromatic series feature and contains in the chlorine derivative according to any one method in the claim 1～4.
6, a class contains the composition of the cyclic oligomer of polydichlorophosphazenes and certain proportion following formula
Figure 891018794_IMG2
N is that 3～5(is included in the formula).
7,, it is characterized in that cyclic oligomer per-cent is approximately 1.5～50% according to the composition of claim 6.
8, according in claim 6 or 7 any one composition and utilize the composition that the method for any one obtains in the claim 1～6.
9, composition according to Claim 8, it obtains 270 ℃ of following polycondensations, and wherein the per-cent of cyclic oligomer is determined by the following relationship formula substantially.
Log (oligopolymer %)=-1.4310 -2(P 2NOCl 5%)+1.726
10, according to any one composition in the claim 6～9, it is characterized in that, with respect to polydichlorophosphazenes and oligopolymer generally speaking, they contain the oligopolymer of about 1.5～50% formula III (n=3,4 and 5 in the formula), and the distribution of these oligopolymer is approximately: the oligopolymer of the oligopolymer of the oligopolymer of 2～10% n=3,15～35% n=4 and 55～75% n=5.
11,, it is characterized in that the easy alkoxy of chlorine atom, aryloxy, alkyl, aryl, sulphur or the amine of polydichlorophosphazenes and oligopolymer replaces according to any one the composition in the claim 6～10.
CN89101879A 1988-03-29 1989-03-29 Preparation contains the polydichlorophosphazenes method for compositions of a certain proportion of cyclic oligomer and the composition that utilizes this method to obtain Pending CN1036546A (en)

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FR8804085A FR2629442B1 (en) 1988-03-29 1988-03-29 PROCESS FOR THE PREPARATION OF POLYDICHLOROPHOSPHAZENES COMPOSITIONS WITH A CONTROLLED RATE OF CYCLIC OLIGOMERS AND THE COMPOSITIONS RESULTING FROM THE IMPLEMENTATION OF THIS PROCESS
FR88.04085 1988-03-29

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FR2466435A1 (en) * 1979-09-27 1981-04-10 Inst Mondial Phosphate NOVEL POLYCHLOROPHOSPHAZENES AND PROCESS FOR THEIR PREPARATION
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JPH01286908A (en) 1989-11-17
DK148389A (en) 1989-09-30
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PT90130A (en) 1989-11-10
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